Hexamethylenetetramine adducts with haloacetonitriles

ABSTRACT

New compositions are made by the 1:1 molar reaction of hexamethylenetetramine with a haloacetonitrile. The quaternary salts thus formed are colorless crystalline solids, readily soluble in water and having biological activity. They are bactericides which also have fungicidal and herbicidal activity.

United States Patent {m 3,624,254

[72] inventor Chester E. Pawloski [50] Field of Search 260/2485 BayCity, Mich. 2 1 App]. 1 ,973 [56] References Cited [22] Filed Mar. 5,1970 UNITED STATES PATENTS [451 Patented NW 1971 3,524,854 8/1970 Kuhn260/2485 [73] Assignee The Dow Chemical Company Midland, Mich PrimaryExammer.lohn M. Ford [54] HEXAMETHYLENETETRAMINE ADDUCTS WITHHALOACETONITRILES 4 Claims, No Drawings [52] US. Cl 260/2485, 424/249[51 1 int. Cl C07d 55/14 Attorneys-Griswold & Burdick and C. E. RehbergABSTRACT: New compositions are made by the 1:1 molar reaction ofhexamethylenetetramine with a haloacetonitrile. The quaternary saltsthus formed are colorless crystalline solids, readily soluble in waterand having biological activity. They are bactericides which also havefungicidal and herbicidal activity.

HEXAMETI-IYLENETETRAMINE ADDUCTS WITI-I HALOACETONITRILES BACKGROUND OFTHE INVENTION Hexamethylenetetramine is known to form quaternary saltadducts with certain halohydrocarbons (Wolf and Scott, US. Pat. No.3,228,829). These adducts show bactericidal and other biologicalactivity.

SUMMARY OF THE INVENTION New, biologically active quaternary salts aremade by the reaction of hexamethylenetetramine (hereinafter, HMTA) witha haloacetonitrile in a lzl molar ratio. These salts are colorless,water-soluble, stable, crystalline compounds having high activity asbactericides as well as other biological activity. These compounds havethe formula N-CHrCEN CH: X

(5H: CH2

SPECIFIC EMBODIMENTS OF THE INVENTION A. Preparation of Compounds,General Procedure Essentially equimolar amounts of HMTA andhaloacetonitrile were dissolved in chloroform, about 1.5-3.5 l. of thelatter being used per g. mole of HMTA. The solutions were stirred atroom temperature for at least 6-8 hr., though the reaction appeared tobe complete in less time. The

products precipitated as colorless crystals as the reaction proceeded.The crystals were separated by filtration and dried in vacuum. Noattempt was made to recover product or unused reactant from thefiltrate. Results are tabulated below.

TABLE I HMTAHaloacetronitrile Salts The compounds of the invention havea wide spectrum of biological activity.

Thus, the compounds of examples I and 3, when incor porated into atypical agar culture medium at a level of 0.05 percent, was percenteffective in preventing the growth of such organisms as Pseudomonasaeroginosa, Staph. aureus, E. coli, B. subtilis, Aerobacter aerogenes,Candida pelliculosa, Salmonella typhosa and Mycobacterium Phlei.

The compound of example 2, in addition to being active against some ofthe above organisms, also showed activity against such diverse organismsas pigweed, apple scab and mouse tapeworm.

I claim:

I. A compound having the formula N N- GH'ICEN CH1 CH2 X f H: C OH: CH?

wherein X is Cl, Br or I.

2. The compound of claim I wherein x is Cl.

3. The compound of claim I wherein X is Br.

4. The compound of claim I wherein X is I.

* i i i

2. The compound of claim 1 wherein x is Cl.
 3. The compound of claim 1wherein X is Br.
 4. The compound of claim 1 wherein X is I.